High-pressure synthesis of metallic perovskite ruthenate CaCu3Ga2Ru2O12

被引:29
作者
Byeon, SH [1 ]
Lee, SS
Parise, JB
Woodward, PM
Hur, NH
机构
[1] Kyung Hee Univ, Coll Environm & Appl Chem, Kyonggi Do 449701, South Korea
[2] SUNY Stony Brook, Dept Geosci, Stony Brook, NY 11794 USA
[3] SUNY Stony Brook, Inst Mineral Phys, Stony Brook, NY 11794 USA
[4] Ohio State Univ, Dept Chem, Columbus, OH 43210 USA
[5] KRISS, Ctr CMR Mat, Taejon 305600, South Korea
关键词
D O I
10.1021/cm049265t
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A new perovskite ruthenate, CaCu3Ga2Ru2O2, has been synthesized at 12.5 GPa and 1200 degreesC and recovered to room pressure and temperature conditions. This oxide is isostructural with CaCu3Ti4O12 and CaCu3Ru4O12, crystallizing in space group Im3 with Ga and Ru. cations disordered over the octahedral sites. CaCu3Ga2Ru2O12 exhibits a temperature-independent Pauli-paramagnetic and metallic character, indicating delocalized electrons for both Cu and Ru. Bond valence calculations based on the refined structure give oxidation states of 2.31 and 4.53 for copper and ruthenium cations, respectively. The itinerant electron behaviour is thought to originate from a significant oxidation of Cu(II) by Ru(V). Such a situation corresponds to Cu(II)-O-Ru(V)<----> Cu(III)-O-Ru(IV) valence degeneracy. This places CaCu3Ga2Ru2O12 among an unusual and interesting group of perovskites that show heteronuclear valence degeneracy.
引用
收藏
页码:3697 / 3701
页数:5
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